Direct synthesis of pentafluoroethyl copper from pentafluoropropionate as an economical C2F5 source: application to pentafluoroethylation of arylboronic acids and aryl bromides.

The direct synthesis of pentafluoroethyl copper (CuC2F5) from a cuprate reagent and ethyl pentafluoropropionate as one of the most economical and useful pentafluoroethyl sources was accomplished. The advantages of this method are; all the reagents employed are low-cost and operationally simple, and the CuC2F5 reagent is prepared in virtually quantitative yield. Furthermore, the CuC2F5 reagent prepared was successfully applied to two types of pentafluoroethylations with arylboronic acids and aryl bromides to provide the pentafluoroethylated aromatic products in good-to-excellent yields, including large scale operations.

[1]  J. Hartwig,et al.  Copper-Mediated Perfluoroalkylation of Heteroaryl Bromides with (phen)CuRF , 2014, Organic letters.

[2]  K. Mikami,et al.  Direct synthesis of a trifluoromethyl copper reagent from trifluoromethyl ketones: application to trifluoromethylation. , 2013, Chemistry.

[3]  J. Vors,et al.  Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation , 2013, Beilstein journal of organic chemistry.

[4]  Y. Itoh,et al.  Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide , 2013, Beilstein journal of organic chemistry.

[5]  J. Benet‐Buchholz,et al.  The critical effect of the countercation in the direct cupration of fluoroform with [Cu(OR)2 ](-). , 2013, Angewandte Chemie.

[6]  M. A. Novikov,et al.  Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: scope, limitations, and mechanistic features. , 2013, The Journal of organic chemistry.

[7]  V. Grushin,et al.  Cupration of C2F5H: isolation, structure, and synthetic applications of [K(DMF)2][(t-BuO)Cu(C2F5)]. Highly efficient pentafluoroethylation of unactivated aryl bromides. , 2013, Journal of the American Chemical Society.

[8]  T. Ritter,et al.  Introduction of fluorine and fluorine-containing functional groups. , 2013, Angewandte Chemie.

[9]  H. Neumann,et al.  Copper-catalyzed trifluoromethylation of aryl- and vinylboronic acids with generation of CF3-radicals. , 2013, Chemical communications.

[10]  N. Sach,et al.  Practical and innate C–H functionalization of heterocycles , 2012, Nature.

[11]  P. Novák,et al.  Trifluoromethylation of α-haloketones. , 2012, Journal of the American Chemical Society.

[12]  P. Novák,et al.  Fluoroform-derived CuCF3 for low-cost, simple, efficient, and safe trifluoromethylation of aryl boronic acids in air. , 2012, Angewandte Chemie.

[13]  M. Beller,et al.  Towards a Practical and Efficient Copper-Catalyzed Trifluoromethylation of Aryl Halides , 2012, Topics in Catalysis.

[14]  J. Hartwig,et al.  A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuR(F)]. , 2012, Angewandte Chemie.

[15]  D. MacMillan,et al.  Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis , 2011, Nature.

[16]  M. A. Novikov,et al.  Direct cupration of fluoroform. , 2011, Journal of the American Chemical Society.

[17]  V. Grushin,et al.  Simple, stable, and easily accessible well-defined CuCF3 aromatic trifluoromethylating agents. , 2011, Angewandte Chemie.

[18]  S. Lindeman,et al.  Copper-catalyzed arylation of 1H-perfluoroalkanes. , 2011, Journal of the American Chemical Society.

[19]  J. Hartwig,et al.  A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides. , 2011, Angewandte Chemie.

[20]  V. Grushin,et al.  Aromatic trifluoromethylation with metal complexes. , 2011, Chemical reviews.

[21]  S. Buchwald,et al.  Room temperature aryl trifluoromethylation via copper-mediated oxidative cross-coupling. , 2011, The Journal of organic chemistry.

[22]  F. Qing,et al.  Copper-mediated oxidative trifluoromethylation of boronic acids. , 2010, Organic letters.

[23]  S. Buchwald,et al.  The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides , 2010, Science.

[24]  jin-quan yu,et al.  Pd(II)-catalyzed ortho-trifluoromethylation of arenes using TFA as a promoter. , 2010, Journal of the American Chemical Society.

[25]  A. I. Mushta,et al.  The solid complex Zn(CF3)Br·2DMF as an alternative reagent for the preparation of both, trifluoromethyl and pentafluoroethyl copper, CuCF3 and CuC2F5 , 2010 .

[26]  V. Petrov Fluorinated Heterocyclic Compounds , 2009 .

[27]  H. Amii,et al.  Aromatic trifluoromethylation catalytic in copper. , 2009, Chemical communications.

[28]  B. Langlois,et al.  Nucleophilic trifluoromethylation of aryl halides with methyl trifluoroacetate , 2007 .

[29]  S. Lynch,et al.  Analysis and manipulation of amphotericin biosynthetic genes by means of modified phage KC515 transduction techniques. , 2004, Gene.

[30]  H. Satō,et al.  6-Substituted 2,2-bis(fluoromethyl)-benzopyran-4-carboxamide K+ channel openers. , 2000, Bioorganic & medicinal chemistry.

[31]  M. Lo,et al.  High-performance liquid chromatographic determination of angiotensin II receptor antagonists in human plasma and urine. I. DuP 532 (L-694,492). , 1992, Journal of chromatography.

[32]  P. Timmermans,et al.  DuP 532: a second generation of nonpeptide angiotensin II receptor antagonists. , 1991, Biochemical and biophysical research communications.

[33]  T. Fuchikami,et al.  A novel and convenient method for trifluoromethylation of organic halides using CF3SiR'3/KF/Cu(I) system , 1991 .

[34]  J. Freskos A Convenient Synthesis of Pentafluoroethyl-Substituted Aromatics , 1988 .

[35]  R. Chambers,et al.  Sodium perfluoroalkane carboxylates as sources of perfluoroalkyl groups , 1988 .